The aim of this research was to study the effect of nonionic and cationic softeners on the thermal degradation of polyethylene terephthalate fibers. The influence of the type of emulsion on the thermal properties and flammability of the resultant samples was investigated by various analytical techniques, namely, differential scanning calorimetry, thermal gravimetric analysis, dynamical mechanical thermal analysis, and the horizontal flammability test. Results showed that softeners with different ionic structure have different effects on thermal degradation and flammability of polyethylene terephthalate substrates.